Method of making gasoline



Feb. 6, 1951 c. E. HEMMINGER METHOD OF MAKING GASOLINE Filed Sept. 18, 1946 PRODUCT T0 RECOVERY m m Ii g M. r, 5 E L w m w s x R 7 b L 7 I 3 0 a r v. mm s E f //V VE N TOR. CHARLES E. HEMM/NGER A TTORNEK Patented Feb. 6, 1951 s PAT'E METHOD OF MAKING GASOLINE Charles E. Hemminger, Westfield, N. 1., assignor to Standard Oil Development Company, a cor:

poration of Delaware Application September 18, 1946, Serial No. 697,807

' 3 Claims.

The present invention relates to improvements in the art of synthesizing hydrocarbons and oxy-- genated hydrocarbons and, more particularly, it relates to a method of carrying out a hydrocarbon synthesis reaction by reacting carbon monoxide and hydrogen so as to obtain maximum utilization of reactants and minimum formation of carbonaceous deposits on the catalyst.

Prior to my invention it was known that hydrocarbons and oxygenated hydrocarbons could be formed by reacting together carbon monoxide and hydrogen in the presence of a suitable catalyst. An early process in this field was known as the Fischer-Tropsch reaction. In the Fischer Tropsch reaction the catalyst generally employed was cobalt carried on-kieselguhr and activated with thoria. Subsequently, a modification of this process was developed in which the catalyst used was-iron. In the iron catalyst method the temperatures and pressures weresomewhat higher than in the earlier Fischer-Tropsch process. The earlier commercial processes for manufacturing hydrocarbons synthetically from carbon monoxide and hydrogen in the presence of a catalyst were carried out me reactor containing a bed (or beds) of stationary catalyst. More recently; research has been directed toward carrying out the hydrocarbon synthesis in what has cometo beknown as the fluid catalyst type of operation. in patents and publications fluid catalyst methods ior'synthesizing hydrocarbons and oxygenated hydrocarbons from carbon monoxide and hydrogen. These disclosures have been of a very superfici'al nature, frequently devoidof any mention of critically significant variables, having confined their teachings to a broad, generaldiscussion of the. usual temperature, pressure and time relationships. While a result may be obtained by following such incomplete teachings, it has been. found that the results are so uncertain in kind and extent and of such doubtful economy as to be of no real practical value to industry. the process of the presentinvention operating variables are carefully co-ordinated during the synthesis of hydrocarbons to give improved results.

The catalyst of the present invention is pref.-v erably powdered iron, although cobalt may be used. 'The iron'catalyst. may, for example, be. formed'by roastinglspent p'yrites catalyst and subsequently reducing, the same in a hydrogen.

atmosphere. Another good catalyst is one which is an essentially pure form ofiron oxide, which oxide is fusedwith' various promoters such as. potassium salts. with. thefurther addition of At the present time, there are disclosed {Claw- 4749.6)

alumina, and then subsequently cooled, ground... and reduced in an atmosphere of hydrogen. This. catalyst for use in a fluid reactor is ground to a. particle size of from 20 to 80 microns with about; 25 per cent within the range of from to 20.

microns. I 7 An important object of my present invention:

is to carry out the hydrocarbon synthesis reac-., tion so as to obtain maximum utilization of the reactants, carbon monoxide and hydrogen.

appended claims".

In general, I carry out the hydrocarbon synthesis in. an operation which is essentially a two,-; stage process in which the major part of the synthesis takes place in the first stage at lower. temperatures and a lower hydrogen to carbon:- monoxide ratio than employed in the second; The synthesis in the second stage takes,

stage. v place,.as stated, with a high hydrogen to carbon monoxide ratio and thisnot only has the efiect. of providing control over the carbon content of. the .catalyst but also converts a considerable. amount of carbon dioxide to hydrocarbon products andwater due to the water gas shift re--- action. Consequently, there is less carbon dioxide'l and hydrogen'rem'aining in the exit gas fromthe second stage, decreasing the volume of gas to the absorption equipment, and giving a higher.

yield of liquid products based on the feed gas. The gas feed to the second stage may or may which will appear morefully hereinafter.

In the accompanying drawing, I have shown.

diagrammaticallya. form of apparatus in which a preferred modification of my invention may be carried into effect.

.Referringin-detail to the drawing, l represents; afprimary ,reactor'containing a fluidized mass. of powdered, catalyst C and 2 is a secondary reactor.' The fresh feed enters the present system through a line 5 and contains hydrogen, carbon. monoxide and a small amount'of carbon dioxidefi theratio of hydrogento carbon monoxide rang-. ing from 1 to 2 mols of hydrogen per mol of car-.

actants are forced into the bottom of reactor 1,

as shown, and thence passed upwardly through a screen or grid G into a mass of fluidized catalyst which, in the drawing, extends in dense phase suspension from G to L, the level L being known commonly in this type of reactor as the upper dense phase level. The catalyst is maintained in the fluidized form or the dense, turbulent suspension mentioned by controlling the superficial velocity of the gases passing upwardly through reactor I within the range of, say, A; to 1 /2 feet per second. Above the level L which is fixed by the amount of catalyst actually present in the reactor, as Well as the superficial velocity of the gasiform material, there is an upper dilute pha's'e suspension of catalyst in ga'siform' material, the concentration of which decreases sharply from the level L to the top of the reactor. In other words, the space from the level L to the top of the reactor is commonly referred to as the'catalys't disengaging space, wherein the suspended catalyst tendsto separate by gravityoutor the gases and/or vapors and descend into -ortoward the dense =-p'has'e suspension. The dense phase suspension using powdered iron catalyst of the particle size mentioned and employing the gas velocities mentioned will have a density of4 to 120 pounds per cubic foot. Ordinarily, in the upper portion'of the-reactor there is disposed a plurality of gas-solid contacting devices It which may be, for example, centrifugal separators through which the gases and/or vapors are forced for the purpose or separating out entrained'catalyst fines, which fines are then returned by one or' iriore dip pipes [-3 to the dense phase suspension. The reaction-products issue from the reactor through line 11 and are-then treated-in a manner which wi-ll-b'e described presently. It is desired to point out that instead of employing'a hindered settling'reactor having a dense phase anda dilute-phase 'of catalyst suspension therein, I may'employ a high speed reactor wherein thesuperficial velocity of the'gases pa'ssing' therethrough maybe ashigh as feetper second, whereupon a single phase suspension is formed within the reactor.

"Since the 'r'eaction between carbon monoxide arid-hydrogen toform hydrocarbons a'nd oxygenated hydrocarbons is highly "exothermic, it is necessaryto abstract heat from the reactor, and to'a'cc'ornplish this, -I-provide"a cooling meansof some-sort 16, which may be, for example, an ordinary tubular heat exchanger, through which is forced a cooling medium, such as *Dowtherm' orwaten'in heat exchange relationship with'tlie catalyst in the'rea'ctionzone.

, Referring again to the crude products in line ll'withdra-wn fromreactor l, the same are passed through a cooling'zon'eifl wherethey are cooled toa'temper'ature of, say, lfiOto 150"F. whereby water and normally liquid'hydrocarbonsare condensed and withdrawn thro'ugha line '25 and delivered to equipment (notshown) fo'r'the purpose-of recovering desired'pro'ducts, suchas the normally liquid hydrocarbons, including gasoline and gas oil, and the oxygenated hydrocarbons,

such as the alcohols, ketones, etc. Since the recovery of the formed hydrocarbon products and the oxygenated hydrocarbon products does not go to the essence of my invention and since the purification and recovery of these substances is known to the prior art, for simplicity I have oinitted a showing of the purificationequipment and a description in words thereof. The gaseous components of the reactionproducts are withdrawn from the cooling'zon'e through 'a line =-that fromSO to '99 per cent of the carbon monoxide fed to the primary reactor is converted under'the'condition's prevailing therein which I shall now disclose. The temperature maintained in reactor I for thisdegree of conversion is 550 to 750 F., the pressure being from 125 to 750 pounds per square inch, preferably 250 to 400 pounds per square inch, and the feed rate being from 20 to 200 volumes of feed gas per pound of ironpresntin tne rea'ctorper' hour. The amount of catalyst presentin therea'ctor, which fixes'the ratio of feed'to catalyst in the 'reactor, is dependent upon the typeand a'ctivityof the catalyst employed. It (the amount of catalyst in the 're-' actor) readjusted-rogue the-desired conversion in the operating rangeof to 99 per cent of carbon monoxide fed to the reactorin the fresh feed. In other words, with a fixed gas feed'to the reactor l under the conditions of temperature and pressure as disclosed herein, the degree of conversion iscOntreIled-by changing the quantity of catalyst-in the reactor. If thedense' phase suspension of a catalyst-- of unknown a'ctivityainounte'd to 30 feet from" G to L- and it-were found that a greater degree of conversion, say,

percent, wasbeing obtained than the-desired 1 degree,-'sayabout 4 Q'O 'pr cent; of the carbon mo'n oxide charged because the-'c atalystwas more-active than anticipated, then the degree of conversion in 'rea'ctor I is-lowered -by decreasing the quantity of c'a-talyst i'n'thereactor, which in'the instance cited would -am'ount to lowering "the upper densephas'e leveFL, say, 10'to 15 feet. 0? course, the'degree" or conversioncould be'lowered by other known means"such'as by increasing the feed rate ofreac'tants,-i.'e., lowering the contact time in'the reactor', or r'educing'th'e temperature.

As stated, the gas infi l isreturned for'further treatment but, accordihg'to 'my invention, it-is returned principally to the secondary reactor-Z containing als'oa quantit pr catalyst preferably inth'eform of a dense phase-suspension extend ing from the screenorgrid Gz'tothe upper dense pha's'e level L2, the-catalyst being procured in the form of a 'dehsephase suspension and an upper dilute phase in precisely the same manner a'sthat described in connection-with the operation of primary reactor l. The gas 'enteri'ngthe secondary reactor '2 'will contain hydrogen, carbon mo'noxideja'nd carbon dioxide primarily, and

the ratio or hydrogen "to carbon monoxide will be 'ofthe'order'of 2 to "2'0 molsof hydrogen per mo'l of carbon mo'noxid'efand the ratio of' carbon dioxide to thec'arbonmorioxide will bein the order of 5 to 1 0 times the volume of carbon monoxide p'res'en't. 'l'Iheratios of hydrogen'and'carb'on dioxide to theca'rbo'n' r'n'onoxi'dej'will depend on controlof several variables as the ratio of hydrogen t'o"carbon monoxide in thefresh feed, the degree of conversion of the carbon monoxide, the "amount-cfrecycie'frcm'line 3'! to reactor l and the addition" of 'watei'toreactor l. The lat. ter twoitemswillbe discussed la'ter. For a '2 to? 1 hydrogen to carbonnionoxi'de fee'dratio, a '95 per cent conversion of carbon monoxide, no recycle of gas. to reactor I and no water added to reactor I, the hydrogen to carbon monoxide ratio will be about 12 and the carbon dioxide to carbon monoxide ratio will be 51.

Some water may be added to stream 31 through line 39 to aid in repressing carbon formation in reactors I- and 2, the water serving to maintain a higher hydrogen .partial pressure in the reactor and to alter the character of the catalyst so that carbon is not formed and laid down on the catalyst in substantial quantities. The amount of gas vented via line 36, which controls the amount of gas in line 31, is fixed so that the volumetric ratio of the quantity of gas in line 31 to the fresh feed gas in line 5 is in the range of 0.2 to 4.0.

p In the reactor 2 the superficial velocity of the gas flowing therethrough is of the same order as that in reactor I but in reactor 2 the temperature may be as much as 100 to 150 higher than in the reactor I and the quantities of gas and catalyst are such in reactor 2 as to give a volume of gas per pound of iron per hour from one-half to onetenth that employed in reactor I, the volume being measured at standard temperature and pressure conditions in both instances. The pressures are maintained in both reactors at essentially the same value. The products issue from the upper portion of reactor 2 after passing through one or more gas-solids contacting devices 40 to separate catalyst fines, pass through a drawoff line 43, discharge into line I4, where they are mixed with the products from reactor I and are delivered therewith to the cooling and recovery systems. The products from reactor 2 may also be withdrawn, all or in part, thru line 2| to a cooling and recovery system similar to 35 and 32.

Catalystpasses from reactor I through a drawoif valved pipe by natural flow into reactor 2. The drawofi pipe 50 is preferably provided with gas leads (not shown) for the purpose of introducing a, fluidizing gas so as to promote ready fiowability by natural flow of catalyst from the reactor I to reactor 2. Catalyst is withdrawn from reactor 2 by drawoff pipe 52 similar to 50 and mixed with a portion of the fresh feed inline 5b to form a suspension which is then conducted pneumatically through line 55 into the bottom of reactor I. A portion of the recycle gas in line 3'! may be withdrawn through line am as a substitute for a portion or all of the fresh feed in line 5a in order to provide a conveying medium for the catalyst returning from reactor 2 to reactor I. This operation also gives recycle of gas in line 31 to reactor I to control reaction conditions therein. This gas may be in the order of 0.01 to 2.0 times the volume of gas in line 5. If desired, the gasiform material in line 30 may be by-passed around the oil scrubber 32 and recycled directly via line 31b and 31 to reactor 2. Another modification of my invention involves withdrawing a portion of the fresh feed in line was attained with an iron type catalyst in the temperature range specified. This equilibrium,=

Again, if the conversion'of carbon monoxide were further increased to 99.5 per cent, the conversion of hydrogen would be 92 per cent. It is apparent from these figures why assumption of the watergas shift equilibrium indicated a greater increase in hydrogen conversion than in the carbon These changes in conversion of the feed components by the water gas monoxide conversion.

shift reaction were postulated on the same operating conditions of temperature, pressure and recycle ratio. vestigation of the range of carbon monoxide conversions at different feed ratios and operating conditions, it was found by me that the water gas shift equilibrium was not attained and that for a given recycle of hydrogen, carbon monoxide and carbon dioxide, after removal of water and normally liquid hydrocarbons by condensation, the conversion of hydrogen changed hand in hand with. the conversion of carbon monoxide. example, when the conversion of carbon mone oxide was increased 10 parts, say, from 89.5. to 99.5 per cent, the conversion of hydrogen was in creased 14 parts, from 71 to per cent hydrogen conversion with the same amount of recycle of carbon dioxide, 0.25 volume of carbon dioxide per volume of hydrogen and carbon monoxide in the fresh feed in each case, the basis of comparison being the CO2 content of the recycle gas. of course, the recycle gas will also contain some H2, CO and perhaps CH4 and other hydrocarbons.

In commercial plants this is of economic importance. CO2, Hz, CO and some light hydrocarbons; are recycled. For comparative purposes I have based the comparison on the CO2 recycled. High hydrogen conversion cannot be obtained by operating at high carbon monoxide conversions, in the order of 99.5 per cent, as indicated by the water gas shift equation. As stated, experimental data has shown only 85 per cent hydrogen conversion compared to 95 per cent calculated by the water oxide and hydrogen in the fresh feed with a hydrogen to carbon monoxide ratio of2. This saving of 84 per cent in recycle gas is of economical importance.

A further advantage of the invention is the controlled carbon formation during a reaction when hydrogen conversions above per cent were obtained. In a single reactor at,.650 FL, to 1 hydrogen to carbon monoxide ratio, 400. pounds persguare inch and 40 volumes of feed,

After extensive experimental in In recycling to a commercial plant,

gas per pounds of cataiyst with. recycleratio inthe order of 4 volumes of recycle per volume-of fresh feed, carbon formation was excessive. For example, in 100 hours the catalyst contained up- Wardly of 50- poun'dsof carbon per 100 pounds of catalyst. At the same time, the catalyst was physio-ally disintegrated by the formation of carbon in the lattice of the catalyst so that the percentage of to 20 microns increased from 5 to 7-5 percent, a very undesirable condition because with this percentage of catalyst fines, the catalyst losses overhead from the reactor are excessive. On-the other hand, it was found that when the conversion of hydrogen was held less than Q3 per cent by practically eliminating the recycle to the first reactor, the carbon forrria ion was decreased to an operable range and catalyst disintegration was avoided. Also, carbon formation in the secondary reactor was found to be negligible because of the high partial pressure of hydrogen present in this reactor.

The invention is not limited to the specific details hereinbefore set forth. For example, (a) two or more single-pass reactors may be used, (0) the first reactor may have a small amount of recycle vent gas feed thereto and the second reactor may be once through, and (c) the first reactor may be once through and the second reactor may use recycle operations. It is also disclosed that successively lower pressures may be used" in each reactor, say, 450' pounds per square inch in the first and 250 pounds per square inch in the second. Again, the recovery systems for the different reactors need not be identical, each having its own condensing system. Finally, the reactors need not have a circulating catalyst stream; in fact, different catalysts may be used in each reactor.

As hereinbefore used, the term recycle gas refers to the normally gaseous portion of the product from which hydrocarbons have been at least partially removed.

Numerous modifications of my invention may be made by those familiar with the art without departing from the spirit thereof.

What I claim is:

1. The. method of synthesizing hydrocarbons which comprises feeding a mixture containing hydrogen and carbon monoxide in the ratio of about 2 mols of hydrogen per mol of carbon monoxide to a reaction zone containing a bed of fluidized powdered iron catalyst, maintaining a temperature in the said reaction zone of from about 600-700 F., maintaining a pressure in said'reaction zone of from 400-450 p. s. i., limitihg the degree of hydrogen conversion not to exceed 90% by causing the reactants to flow throughthe reaction zone at a space velocity of from 10-200 volumes of feed gas per pound of catalyst per hour and including added water in the feed, whereby carbonaceous material is deposited on said catalyst, withdrawing the crude reaction products and unconverted synthesis gas from the reaction zone, cooling. the product to condense water and at least a major portion of the normally liquid. hydrocarbons, delivering uncondensed gases containing. hydrogen, carbon monoxide and carbon dioxide in the ratio of about 2 to volumes of hydrogen per volume of carbon monoxide and 5 to 10 volumesof carbon dioxide per volume of carbon monoxide and vapors with fresh feed to a second reactor containing a bed of fluidized iron catalyst, passing atleast a portion of said carbon-containing catalyst from said primary reaction zone to said sec- 0nd reactionzone, maintaining a temperature in:

the said second reaction zone from E; higher than that prevailing in the first named re action zone reacting said carbon dioxide with said carbon-contaminated catalyst in said second reaction zone whereby the carbon content of said catalyst in said second reaction zone is reduced to a value substantially below the carbon contenton catalyst in said primary reaction zone and whereby a substantial portion of said carbon di oxide is converted to carbon monoxide in said second reaction zone, maintaining further hydrocarbon synthesis in said second reaction zone with carbon monoxide present in said feed to said:

zone and CO formed as a result of interaction of carbon dioxide in said feed with said carbon containing catalyst, permitting the reactants to remain resident in the said second reaction zone for a period of time suflicient to effect conversion to the extent that at least 93% of the total carbon monoxide and hydrogen fed to the system are converted to hydrocarbons and oxygenated hydrocarbons, withdrawing catalyst from said sec-' ond reaction zone and returning at least a portion. of the thus withdrawn catalyst to the first reaction zone. 2. The process of synthesizing hydrocarbons which comprises feeding a gas mixture containing H2 and CO in the ratio of about 1 to 2 mols. l-lzv per mol CO into a primary reaction zone contain: ing a bed of fluidized powdered iron catalyst, maintaining a temperature in said reaction zone of. from about 550 to 750 F. and, a pressure from about 250 to about 450 p. si., passing said. rea,ctants through said reaction zone at a space ve locity of from about 10 to 200 volumes of feed.

second hydrocarbon synthesis reaction zone, said tail gas containing substantial proportions of carbon dioxide, passing at least a portion. of said carbon-containing catalyst from said primary reaction zone to said second reaction zone, main-.

' taining a fluidized bed of saidiron catalyst in said second reaction zone, maintaining a temperature in said second reaction zone of from.100 to 150 higher than that prevailing in said first-named reaction zone, reacting said carbon dioxide with said carbon-contaminatedcatalyst insaidsecond reactionzone whereby thecarbon contentof said catalyst in said second reaction zone is reducedto a value substantially below the carbon content in saidprimary reaction zone andwhereby a substantial portion of said carbon dioxide is converted to carbon monoxide in said second reaction zone, maintaining further hydrocarbon synthesis to effect conversion to the. extent that at least 93% of the total carbon monoxide and hydrogen fed to the system is converted to hydrocarbons and oxygenated hydrocarbons, Withdrawing catalyst from said second reaction zone and returning at least a portionof thethus withdrawncatalyst.

75 to the first reaction zone.

3. The process of claim 2 wherein said tail gas fed to said second hydrocarbon synthesis zone comprises hydrogen, carbon monoxide and carbon dioxide and wherein the Hz/CO ratio is from about 2-20/1 and wherein the CO2/CO ratio is 5 from about 5-10/1.

CHARLES E. HEMMING-ER.

REFERENCES CITED The following references are of record in the 10 file of this patent:

Number 10 UNITED STATES PATENTS Name Date Fischer Mar. 7, 1939 Atwell Nov. 7, 1939 Murphree Sept. 23, 1941 Atwell Oct. 15, 1946 Huber, Jr Mar. 11, 1947 Scharmann Oct. 19, 1948 

1. THE METHOD OF SYNTHESIZING HYDROCARBONS WHICH COMPRISES FEEDING A MIXTURE CONTAINING HYDROGEN AND CARBON MONOXIDE IN THE RATIO OF ABOUT 2 MOLS OF HYDROGEN PER MOL OF CARBON MONOXIDE TO A REACTION ZONE CONTAINING A BED OF FLUIDIZED POWDERED IRON CATALYST, MAINTAINING A TEMPERATURE IN THE SAID REACTION ZONE OF FROM ABOUT 600*-700* F., MAINTAINING A PRESSURE IN SAID REACTION ZONE OF FROM 400-450 P. S. I., LIMITING THE DEGREE OF HYDROGEN CONVERSION NOT TO EXCEED 90% BY CAUSING THE REACTANTS TO FLOW THROUGH THE REACTION ZONE AT A SPACE VELOCITY OF FROM 10-200 VOLUMES OF FEED GAS PER POUND OF CATALYST PER HOUR AND INCLUDING ADDED WATER IN THE FEED, WHEREBY CARBONACEOUS MATERIAL IS DEPOSITED ON SAID CATALYST, WITHDRAWING THE CRUDE REACTION PRODUCTS AND UNCONVERTED SYNTHESIS GAS FROM THE REACTION ZONE, COOLING THE PRODUCT TO CONDENSE WATER AND AT LEAST A MAJOR PORTION OF THE NORMALLY LIQUID HYDROCARBONS, DELIVERING UNCONDENSED GASES CONTAINING HYDROGEN, CARBON MONOXIDE AND CARBON DIOXIDE IN THE RATIO OF ABOUT 2 TO 20 VOLUMES OF HYDROGEN PER VOLUME OF CARBON MONOXIDE AND 5 TO 10 VOLUMES OF CARBON DIOXIDE PER VOLUME OF CARBON MONOXIDE AND VAPORS WITH FRESH FEED TO A SECOND REACTOR CONTAINING A BED OF FLUIDIZED IRON CATALYST, PASSING AT LEAST A PORTION OF SAID CARBON-CONTAINING CATALYST FROM SAID PRIMARY REACTION ZONE TO SAID SECOND REACTION ZONE, MAINTAINING A TEMPERATURE IN THE SAID SECOND REACTION ZONE FROM 100*-150* F. HIGHER THAN THAT PREVAILING IN THE FIRST NAMED REACTION ZONE REACTING SAID CARBON DIOXIDE WITH SAID CARBON-CONTAMINATED CATALYST IN SAID SECOND REACTION ZONE WHEREBY THE CARBON CONTENT OF SAID 